Substrate processing method, composition for forming metal-containing resist, metal-containing resist, and substrate processing system

Abstract

Provided is a substrate processing method. The method comprises a step (a) for providing a substrate having a base film, and a step (b) for forming a metal-containing resist film on the base film by using a polyfunctional compound and a metal-containing precursor having a photosensitive group.

Description

Substrate processing method, metal-containing resist-forming composition, metal-containing resist, and substrate processing system

[0001] SUMMARY Exemplary embodiments of the present disclosure relate to a substrate processing method, a metal-containing resist-forming composition, a metal-containing resist, and a substrate processing system.

[0002] Japanese Patent Application Laid-Open No. 2003-124222 discloses a technique for forming a thin film that can be patterned on a semiconductor substrate using extreme ultraviolet light (hereinafter referred to as EUV).

[0003] Special Publication No. 2021-523403

[0004] The present disclosure provides techniques for adjusting the composition of a metal-containing resist film formed on a substrate.

[0005] In one exemplary embodiment of the present disclosure, there is provided a substrate processing method including the steps of: (a) providing a substrate having an underlayer; and (b) forming a metal-containing resist film on the underlayer using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0006] According to one exemplary embodiment of the present disclosure, a technique for adjusting the composition of a metal-containing resist film formed on a substrate can be provided.

[0007] FIG. 1 is a diagram for explaining an example of the configuration of a heat treatment system. FIG. 2 is a diagram for explaining an example of the configuration of a plasma treatment system. FIG. 3 is a diagram for explaining an example of the configuration of a capacitively coupled plasma treatment apparatus. FIG. 4 is a diagram for explaining an example of the configuration of a liquid treatment system. FIG. 5 is a flowchart showing the present treatment method. FIG. 6 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. 7 is a diagram showing an example of an undercoat film UF of a substrate W. FIG. 8 is a diagram showing an example of a cross-sectional structure of a substrate W on which a metal-containing resist film RM is formed. FIG. 9 is a flowchart showing an example of a process ST2 using the ALD method. FIG. 10 is a flowchart showing an example of a process ST2 using the ALD method. FIG. 11 is a diagram schematically showing an example of a phenomenon occurring on the surface of a substrate W in a process ST2 using the ALD method. FIG. 12 is a block diagram for explaining an example of the configuration of a substrate treatment system SS. FIG. 13 is a flowchart showing a method MT.

[0008] Hereinafter, each embodiment of the present disclosure will be described.

[0009] In one exemplary embodiment, a substrate processing method is provided, the substrate processing method comprising the steps of: (a) providing a substrate having an underlayer; and (b) forming a metal-containing resist film on the underlayer using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0010] In one exemplary embodiment, the metal-containing precursor comprises a compound (α) having an amine group and / or an alkoxy group.

[0011] In one exemplary embodiment, the compound (α) includes a compound (α1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

[0012] In one exemplary embodiment, the compound (α1) contains Sn.

[0013] In one exemplary embodiment, the photosensitive group is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and —CH ｘ F ｙ (wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3).

[0014] In one exemplary embodiment, the polyfunctional compound comprises at least one compound (β) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

[0015] In one exemplary embodiment, in step (b), H ２ O, H ２ O ２ , O ３ , and O ２ At least one selected from the group consisting of:

[0016] In one exemplary embodiment, the step (b) includes: (b1) supplying a gas containing a metal-containing precursor onto an underlayer film to form a metal-containing precursor film; and (b2) supplying a gas containing a polyfunctional compound to the metal-containing precursor film to form a metal-containing resist film from the metal-containing precursor film.

[0017] In one exemplary embodiment, steps (b1) and (b2) are repeated multiple times.

[0018] In one exemplary embodiment, step (b) includes forming a metal-containing resist film using a gas mixture including a metal-containing precursor and a polyfunctional compound.

[0019] In one exemplary embodiment, the metal-containing precursor comprises a metal complex comprising at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

[0020] In one exemplary embodiment, the polyfunctional compound comprises at least one compound (β) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

[0021] In one exemplary embodiment, step (b) includes applying a solution containing a metal-containing precursor and a polyfunctional compound onto the undercoat film, and heating the applied solution to form a metal-containing resist film.

[0022] In one exemplary embodiment, the substrate processing method further includes (c) exposing the substrate after step (b) to form exposed first regions and unexposed second regions in the metal-containing resist film; and (d) developing the substrate to selectively remove the second regions from the metal-containing resist film.

[0023] In one exemplary embodiment, in step (d), the second region is removed by a developing gas or liquid containing a weak acid.

[0024] In one exemplary embodiment, the weak acid comprises an organic acid with a pKa<16.

[0025] In one exemplary embodiment, the organic acid comprises at least one selected from the group consisting of an alcohol, a thiol, a carboxylic acid, a sulfonic acid, a β-diketone, an alkyl carbonate, and an azole.

[0026] In one exemplary embodiment, there is provided a metal-containing resist-forming composition comprising a metal-containing precursor having a photosensitive group and a polyfunctional compound, wherein the metal-containing precursor comprises a compound having the photosensitive group and an amine group and / or an alkoxy group.

[0027] In one exemplary embodiment, there is provided a metal-containing resist comprising a compound having a repeating unit represented by the following formula (1) in its molecule: -(M-X-A-X)- (1) (in the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from a terminal functional group of a polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate, and A represents a divalent organic group having from 2 to 10 carbon atoms).

[0028] In one exemplary embodiment, there is provided a substrate processing system having one or more substrate processing apparatuses and a controller, wherein the controller is configured to control the one or more substrate processing apparatuses to (a) provide a substrate having an underlayer film, and (b) form a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a multifunctional compound.

[0029] In one exemplary embodiment, there is provided a developing method including the steps of: (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film; (b) exposing the metal-containing resist through an exposure mask to form an exposed first region and an unexposed second region in the metal-containing resist; and (c) selectively removing one of the first region and the second region, wherein the metal-containing resist in the step (a) contains a compound having a repeating unit represented by the following formula (1) in its molecule: -(M-X-A-X)- (1) (in the above formula (1), M represents Sn, Ti, Hf, Zr, or In; X represents a divalent group derived from a terminal functional group of a polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate; and A represents a divalent organic group having from 2 to 10 carbon atoms).

[0030] In one exemplary embodiment, there is provided an etching method including: (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film, wherein the metal-containing resist has at least one opening; and (b) etching the undercoat film through the opening, wherein the metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in its molecule: -(M-X-A-X)- (1) (in the above formula (1), M represents Sn, Ti, Hf, Zr, or In; X represents a divalent group derived from a terminal functional group of a polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate; and A represents a divalent organic group having from 2 to 10 carbon atoms).

[0031] Hereinafter, each embodiment of the present disclosure will be described in detail with reference to the drawings. In each drawing, the same or similar elements are designated by the same reference numerals, and redundant explanations will be omitted. Unless otherwise specified, the positional relationships, such as up, down, left, and right, will be described based on the positional relationships shown in the drawings. The dimensional ratios in the drawings do not represent actual ratios, and the actual ratios are not limited to the ratios shown in the drawings.

[0032] The substrate processing method according to the present disclosure may be performed by a substrate processing system. In one embodiment, the substrate processing system includes one or more substrate processing apparatuses and a controller, and the controller is configured to control the one or more substrate processing apparatuses to (a) provide a substrate having an underlayer film, and (b) form a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a multifunctional compound. The substrate processing system according to the present disclosure may include a thermal processing system, a plasma processing system, a liquid processing system, etc.

[0033] 1 is a diagram illustrating an example of the configuration of a heat treatment system. In one embodiment, the heat treatment system includes a heat treatment apparatus 100 and a control unit 200. The heat treatment system is an example of a substrate processing system, and the heat treatment apparatus 100 is an example of a substrate processing apparatus.

[0034] The heat treatment apparatus 100 has a processing chamber 102 configured to be able to form a sealed space. The processing chamber 102 is, for example, an airtight cylindrical container configured to be able to adjust the internal atmosphere. A sidewall heater 104 is provided on the sidewall of the processing chamber 102. A ceiling heater 130 is provided on the ceiling wall (top plate) of the processing chamber 102. A ceiling surface 140 of the ceiling wall (top plate) of the processing chamber 102 is formed as a horizontal, flat surface, and its temperature is adjusted by the ceiling heater 130.

[0035] A substrate support 121 is provided at the lower side of the processing chamber 102. The substrate support 121 has a substrate support surface on which a substrate W is supported. The substrate support 121 is formed, for example, in a circular shape in a plan view, and the substrate W is placed on its horizontally formed surface (top surface). A stage heater 120 is embedded within the substrate support 121. This stage heater 120 can heat the substrate W placed on the substrate support 121. A ring assembly (not shown) may be arranged on the substrate support 121 to surround the substrate W. The ring assembly may include one or more annular members. By arranging the ring assembly around the substrate W, temperature controllability in the outer peripheral region of the substrate W can be improved. The ring assembly may be made of an inorganic material or an organic material depending on the desired thermal treatment.

[0036] The substrate support 121 is supported in the processing chamber 102 by support columns 122 provided on the bottom surface of the processing chamber 102. A plurality of lift pins 123 that can be raised and lowered vertically are provided on the circumferential outer sides of the support columns 122. Each of the lift pins 123 is inserted into a through hole provided in the substrate support 121. The lift pins 123 are arranged at intervals in the circumferential direction. The lifting and lowering operation of the lift pins 123 is controlled by a lifting mechanism 124. When the lift pins 123 protrude from the surface of the substrate support 121, the substrate W can be transferred between a transport mechanism (not shown) and the substrate support 121.

[0037] An exhaust port 131 having an opening is provided in the sidewall of the processing chamber 102. The exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe. The exhaust mechanism 132 is composed of a vacuum pump, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131. The pressure inside the processing chamber 102 is adjusted by adjusting the exhaust flow rate, etc., using the exhaust mechanism 132. Note that a transfer port for a substrate W (not shown) is formed in the sidewall of the processing chamber 102 at a position different from the position where the exhaust port 131 opens, so as to be able to be opened and closed freely.

[0038] Furthermore, a gas nozzle 141 is provided on the sidewall of the processing chamber 102 at a position different from the exhaust port 131 and the transfer port for the substrate W. The gas nozzle 141 supplies a processing gas into the processing chamber 102. The gas nozzle 141 is provided on the sidewall of the processing chamber 102 on the opposite side from the exhaust port 131 when viewed from the center of the substrate support 121. That is, the gas nozzle 141 is provided on the sidewall of the processing chamber 102 symmetrically to the exhaust port 131 with respect to a vertical imaginary plane that passes through the center of the substrate support 121.

[0039] The gas nozzle 141 is formed in a rod shape that protrudes from the sidewall of the processing chamber 102 toward the center of the processing chamber 102. The tip of the gas nozzle 141 extends, for example, horizontally from the sidewall of the processing chamber 102. The processing gas is discharged into the processing chamber 102 from a discharge port opening at the tip of the gas nozzle 141, flows in the direction of the dashed-dotted arrow shown in FIG. 1 , and is exhausted from the exhaust port 131. The tip of the gas nozzle 141 may have a shape that extends obliquely downward toward the substrate W, or may have a shape that extends obliquely upward toward the ceiling surface 140 of the processing chamber 102.

[0040] The gas nozzle 141 may be provided, for example, on the ceiling wall of the processing chamber 102. The exhaust port 131 may be provided on the bottom surface of the processing chamber 102.

[0041] The heat treatment apparatus 100 has a gas supply pipe 152 connected to a gas nozzle 141 from outside the processing chamber 102. A pipe heater 160 for heating the gas in the gas supply pipe is provided around the gas supply pipe 152. The gas supply pipe 152 is connected to a gas supply unit 170. The gas supply unit 170 includes at least one gas source and at least one flow rate controller. The gas supply unit may include a vaporizer that vaporizes a liquid material.

[0042] The control unit 200 processes computer-executable instructions that cause the heat treatment apparatus 100 to perform the various steps described in this disclosure. The control unit 200 may be configured to control each element of the heat treatment apparatus 100 to perform the various steps described herein. In one embodiment, part or all of the control unit 200 may be included in the heat treatment apparatus 100. The control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3. The control unit 200 is realized, for example, by the computer 200a. The processing unit 200a1 may be configured to read a program from the storage unit 200a2 and execute the read program to perform various control operations. This program may be stored in the storage unit 200a2 in advance or may be acquired via a medium when needed. The acquired program is stored in the storage unit 200a2 and read from the storage unit 200a2 by the processing unit 200a1 and executed. The medium may be various storage media readable by the computer 200a, or a communication line connected to the communication interface 200a3. The processing unit 200a1 may be a CPU (Central Processing Unit). The storage unit 200a2 may include a RAM (Random Access Memory), a ROM (Read Only Memory), a HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof. The communication interface 200a3 may communicate with the heat treatment apparatus 100 via a communication line such as a LAN (Local Area Network).

[0043] <Configuration Example of Plasma Processing System> FIG. 2 is a diagram illustrating a configuration example of a plasma processing system. In one embodiment, the plasma processing system includes a plasma processing device 1 and a control unit 2. The plasma processing system is an example of a substrate processing system, and the plasma processing device 1 is an example of a substrate processing device. The plasma processing device 1 includes a plasma processing chamber (hereinafter simply referred to as a "processing chamber") 10, a substrate support 11, and a plasma generation unit 12. The plasma processing chamber 10 has a plasma processing space. The plasma processing chamber 10 also has at least one gas supply port for supplying at least one processing gas to the plasma processing space and at least one gas exhaust port for exhausting gas from the plasma processing space. The gas supply port is connected to a gas supply unit 20 (described later), and the gas exhaust port is connected to an exhaust system 40 (described later). The substrate support 11 is disposed in the plasma processing space and has a substrate support surface for supporting a substrate.

[0044] The plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space. The plasma formed in the plasma processing space may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), electron-cyclotron-resonance plasma (ECR plasma), helicon wave plasma (HWP), or surface wave plasma (SWP). Various types of plasma generators may be used, including alternating current (AC) plasma generators and direct current (DC) plasma generators. In one embodiment, the AC signal (AC power) used in the AC plasma generator has a frequency in the range of 100 kHz to 10 GHz. Thus, AC signals include radio frequency (RF) signals and microwave signals. In one embodiment, the RF signal has a frequency in the range of 100 kHz to 150 MHz.

[0045] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various steps described in this disclosure. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform the various steps described herein. In one embodiment, part or all of the control unit 2 may be included in the plasma processing apparatus 1. The control unit 2 is realized by, for example, a computer 2a. The control unit 2 may include a processing unit 2a1, a storage unit 2a2, and a communication interface 2a3. Each component of the control unit 2 may be similar to each component of the control unit 200 (see FIG. 1) described above.

[0046] The following describes a configuration example of a capacitively coupled plasma processing apparatus as an example of the plasma processing apparatus 1. Fig. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.

[0047] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support 11 and a gas inlet. The gas inlet is configured to introduce at least one process gas into the plasma processing chamber 10. The gas inlet includes a showerhead 13. The substrate support 11 is disposed within the plasma processing chamber 10. The showerhead 13 is disposed above the substrate support 11. In one embodiment, the showerhead 13 forms at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the showerhead 13, a sidewall 10a of the plasma processing chamber 10, and the substrate support 11. The plasma processing chamber 10 is grounded. The showerhead 13 and the substrate support 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0048] The substrate support 11 includes a main body 111 and a ring assembly 112. The main body 111 has a central region 111a for supporting a substrate W and an annular region 111b for supporting the ring assembly 112. A wafer is an example of a substrate W. The annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in a plan view. The substrate W is disposed on the central region 111a of the main body 111, and the ring assembly 112 is disposed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also called a substrate support surface for supporting the substrate W, and the annular region 111b is also called a ring support surface for supporting the ring assembly 112.

[0049] In one embodiment, the main body 111 includes a base 1110 and an electrostatic chuck 1111. The base 1110 includes a conductive member. The conductive member of the base 1110 can function as a lower electrode. The electrostatic chuck 1111 is disposed on the base 1110. The electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a. The ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that the annular region 111b may also be provided by another member surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member. In this case, the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member. Furthermore, at least one RF / DC electrode coupled to an RF power supply 31 and / or a DC power supply 32, which will be described later, may be disposed within the ceramic member 1111a. In this case, the at least one RF / DC electrode functions as a lower electrode. When a bias RF signal and / or a DC signal, which will be described later, is supplied to the at least one RF / DC electrode, the RF / DC electrode is also called a bias electrode. Note that the conductive member of the base 1110 and the at least one RF / DC electrode may function as multiple lower electrodes. Furthermore, the electrostatic electrode 1111b may function as a lower electrode. Therefore, the substrate support 11 includes at least one lower electrode.

[0050] The ring assembly 112 includes one or more annular members. In one embodiment, the one or more annular members include one or more edge rings and at least one cover ring. The edge rings are formed of a conductive or insulating material, and the cover rings are formed of an insulating material.

[0051] The substrate support 11 may also include a temperature adjustment module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature. The temperature adjustment module may include a heater, a heat transfer medium, a flow passage 1110a, or a combination thereof. A heat transfer fluid such as brine or a gas flows through the flow passage 1110a. In one embodiment, the flow passage 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111. The substrate support 11 may also include a heat transfer gas supply configured to supply a heat transfer gas to a gap between the backside of the substrate W and the central region 111a.

[0052] The showerhead 13 is configured to introduce at least one process gas from the gas supply unit 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and multiple gas inlets 13c. The process gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the multiple gas inlets 13c. The showerhead 13 also includes at least one upper electrode. In addition to the showerhead 13, the gas inlet may also include one or more side gas injectors (SGIs) attached to one or more openings formed in the sidewall 10a.

[0053] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In one embodiment, the gas supply unit 20 is configured to supply at least one process gas from a corresponding gas source 21 to the showerhead 13 via a corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller. Additionally, the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of the at least one process gas.

[0054] The power supply 30 includes an RF power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The RF power supply 31 is configured to supply at least one RF signal (RF power) to at least one lower electrode and / or at least one upper electrode. This generates a plasma from at least one processing gas supplied to the plasma processing space 10s. Therefore, the RF power supply 31 can function as at least a part of the plasma generation unit 12. Furthermore, by supplying a bias RF signal to the at least one lower electrode, a bias potential is generated on the substrate W, thereby attracting ion components in the formed plasma to the substrate W.

[0055] In one embodiment, the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b. The first RF generating unit 31a is coupled to at least one lower electrode and / or at least one upper electrode via at least one impedance matching circuit and is configured to generate a source RF signal (source RF power) for plasma generation. In one embodiment, the source RF signal has a frequency in the range of 10 MHz to 150 MHz. In one embodiment, the first RF generating unit 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and / or at least one upper electrode.

[0056] The second RF generator 31b is coupled to at least one lower electrode via at least one impedance matching circuit and is configured to generate a bias RF signal (bias RF power). The frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency lower than the frequency of the source RF signal. In one embodiment, the bias RF signal has a frequency in the range of 100 kHz to 60 MHz. In one embodiment, the second RF generator 31b may be configured to generate multiple bias RF signals having different frequencies. The generated one or more bias RF signals are supplied to at least one lower electrode. In various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0057] The power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generator 32a and a second DC generator 32b. In one embodiment, the first DC generator 32a is connected to the at least one lower electrode and configured to generate a first DC signal. The generated first DC signal is applied to the at least one lower electrode. In one embodiment, the second DC generator 32b is connected to the at least one upper electrode and configured to generate a second DC signal. The generated second DC signal is applied to the at least one upper electrode.

[0058] In various embodiments, the first and second DC signals may be pulsed. In this case, a sequence of voltage pulses is applied to at least one lower electrode and / or at least one upper electrode. The voltage pulses may have a rectangular, trapezoidal, triangular, or combination thereof pulse waveform. In one embodiment, a waveform generator for generating the sequence of voltage pulses from the DC signal is connected between the first DC generator 32a and at least one lower electrode. Thus, the first DC generator 32a and the waveform generator constitute a voltage pulse generator. When the second DC generator 32b and the waveform generator constitute a voltage pulse generator, the voltage pulse generator is connected to at least one upper electrode. The voltage pulses may have either positive or negative polarity. Furthermore, the sequence of voltage pulses may include one or more positive voltage pulses and one or more negative voltage pulses within one period. The first and second DC generating units 32a and 32b may be provided in addition to the RF power supply 31, or the first DC generating unit 32a may be provided instead of the second RF generating unit 31b.

[0059] The exhaust system 40 may be connected to, for example, a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s is regulated by the pressure regulating valve. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0060] 4 is a diagram illustrating an example of the configuration of a liquid processing system. In one embodiment, the liquid processing system includes a liquid processing apparatus 300 and a control unit 400. The liquid processing system is an example of a substrate processing system, and the liquid processing apparatus 300 is an example of a substrate processing apparatus.

[0061] 4, the liquid processing apparatus 300 has a spin chuck 311 as a substrate support within a processing chamber 310. The spin chuck 311 holds the substrate W horizontally. The spin chuck 311 is connected to a rotating part 312 that can be raised and lowered, and the rotating part 312 is connected to a rotation driving part 313 that is constituted by a motor or the like. The substrate W held by the spin chuck 311 can be rotated by driving the rotation driving part 313.

[0062] A cup 321 is disposed outside the spin chuck 311 to prevent processing liquid (resist liquid, developer liquid, cleaning liquid, etc.) and mist of the processing liquid from scattering around the cup 321. A drain pipe 323 and an exhaust pipe 324 are provided at a bottom 322 of the cup 321. The drain pipe 323 is connected to a drainage device 325 such as a drainage pump. The exhaust pipe 324 is connected via a valve 326 to an exhaust device 327 such as an exhaust pump.

[0063] An air blower 314 is provided at the top of processing chamber 310 of liquid processing apparatus 300 to supply air at a required temperature and humidity as a downflow into cup 321 .

[0064] A processing liquid supply nozzle 331 is used to form a puddle of processing liquid on the substrate W. This processing liquid supply nozzle 331 is provided on a nozzle support 332, such as an arm, which can be moved up and down by a drive mechanism as indicated by a reciprocating dashed arrow A in the figure, and can also be moved horizontally as indicated by a reciprocating dashed arrow B. A processing liquid (such as a resist liquid or a developer) is supplied to the processing liquid supply nozzle 331 from a processing liquid supply source 334 via a supply pipe 333.

[0065] When forming a puddle, if a so-called long nozzle having an outlet whose length is equal to or greater than the diameter of the substrate W is used, a puddle of processing liquid can be formed on the substrate W by scanning the nozzle from one end to the other end over the substrate W. In the case of a so-called straight-type nozzle that discharges liquid so as to form a liquid column whose width is sufficiently small compared to the diameter of the substrate W, the outlet can be positioned above the center of the substrate W and the processing liquid can be discharged while rotating the substrate W, thereby spreading the processing liquid over the entire surface of the substrate W and forming a puddle of processing liquid on the substrate W. In addition, a puddle of processing liquid can be formed by scanning a straight-type nozzle over the substrate W in the same manner as a long nozzle, or by arranging multiple outlets for discharging liquid above the substrate W as in the case of a straight-type nozzle and supplying the processing liquid from each of the outlets.

[0066] Gas nozzle 341 has nozzle body 342. Nozzle body 342 is attached to a nozzle support such as an arm, and the nozzle support can be moved up and down by a drive mechanism as indicated by the dashed reciprocating arrow C in the figure, and can also be moved horizontally as indicated by the dashed reciprocating arrow D.

[0067] The gas nozzle 341 has two nozzle outlets 343 and 344. The nozzle outlets 343 and 344 are formed by branching off from a gas flow path 345. The gas flow path 345 is connected to a gas supply source 347 via a gas supply pipe 346. An inert gas or a non-oxidizing gas, such as nitrogen gas, is prepared in the gas supply source 347. When nitrogen gas, for example, is supplied from the gas flow path 345 to the gas nozzle 341, the nitrogen gas is discharged from each of the nozzle outlets 343 and 344.

[0068] The gas nozzle 341 is also provided with a cleaning liquid supply nozzle 351 that cleans the substrate W with the processing liquid after liquid processing. The cleaning liquid supply nozzle 351 is connected to a cleaning liquid supply source 353 via a cleaning liquid supply pipe 352. Pure water, for example, is used as the cleaning liquid. The cleaning liquid supply nozzle 351 is located between the two nozzle outlets 343 and 344 described above, but the location is not limited to this. The cleaning liquid supply nozzle 351 may be configured independent of the gas nozzle 341.

[0069] The controller 400 processes computer-executable instructions that cause the liquid treatment device 300 to perform the various steps described in this disclosure. The controller 400 may be configured to control each element of the liquid treatment device 300 to perform the various steps described herein. In one embodiment, part or all of the controller 400 may be included in the liquid treatment device 300. The controller 400 is realized by, for example, a computer 400a. The computer 400a may include a processing unit 400a1, a memory unit 400a2, and a communication interface 400a3. Each component of the controller 400 may be similar to each component of the controller 200 (see FIG. 1) described above.

[0070] <Example of Substrate Processing Method> FIG. 5 is a flowchart showing a substrate processing method (hereinafter also referred to as "this processing method") according to an illustrative embodiment. This processing method includes step ST1 of providing a substrate having an underlayer film and step ST2 of forming a metal-containing resist film on the underlayer film. In one embodiment, the formation process of the metal-containing resist film (hereinafter also referred to as "film formation process") in step ST2 is performed by a dry process (hereinafter also referred to as "dry film formation") using a process gas. In one embodiment, the film formation process in step ST2 is performed by a wet process (hereinafter also referred to as "wet film formation") using a solution. In one embodiment, the film formation process in step ST2 is performed using both wet film formation and dry film formation.

[0071] This processing method may include (a) a step of providing a substrate having an underlayer film (corresponding to "step ST1" described below); and (b) a step of forming a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound (corresponding to "step ST2" described below). Each step may be performed using one of the substrate processing systems described above (see FIGS. 1 to 4 ), or may be performed using two or more of these substrate processing systems. For example, this processing method may be performed in a heat treatment system (see FIG. 1 ). The following description will be given taking as an example a case where the control unit 200 controls each unit of the heat treatment apparatus 100 to perform this processing method on a substrate W.

[0072] (Process ST1: Providing a Substrate) First, in process ST1, a substrate W is provided into the process chamber 102 of the heat treatment apparatus 100. The substrate W is provided onto the substrate support 121 via the lift pins 123. After the substrate W is placed on the substrate support 121, the temperature of the substrate support 121 is adjusted to a set temperature. The set temperature may be, for example, 350°C or less, or may be a temperature between 25°C and 350°C. The temperature of the substrate support 121 may be adjusted by controlling the output of one or more heaters selected from the sidewall heater 104, the stage heater 120, the ceiling heater 130, and the piping heater 160 (hereinafter collectively referred to as "each heater"). In this processing method, the temperature of the substrate support 121 may be adjusted to the set temperature before process ST1. That is, the substrate W may be provided on the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.

[0073] The substrate W may be used in the manufacture of semiconductor devices. Examples of semiconductor devices include semiconductor memory devices such as DRAMs and 3D-NAND flash memories, and logic devices. The substrate W has an underlayer UF. The underlayer UF may be an organic film, a dielectric film, a metal film, a semiconductor film, or a laminate film thereof formed on a silicon wafer. In one embodiment, the underlayer UF includes, for example, at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.

[0074] 6 and 7 are diagrams showing examples of an undercoat film UF of a substrate W. As shown in Fig. 6, the undercoat film UF may be composed of a first film UF1, a second film UF2, and a third film UF3. As shown in Fig. 7, the undercoat film UF may be composed of the second film UF2 and the third film UF3. In one embodiment, the undercoat film UF may be subjected to a surface modification treatment.

[0075] The first film UF1 is, for example, a spin-on-glass (SOG) film, a SiC film, a SiON film, a Si-containing antireflective coating (SiARC), or an organic film. The second film UF2 is, for example, a spin-on-carbon (SOC) film, an amorphous carbon film, or a silicon-containing film. The third film UF3 is, for example, a silicon-containing film. The silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbonitride film, a polycrystalline silicon film, or a carbon-containing silicon film. The third film UF3 may be composed of multiple types of stacked silicon-containing films. For example, the third film UF3 may be composed of alternating stacked silicon oxide films and silicon nitride films. The third film UF3 may also be composed of stacked silicon oxide films and polycrystalline silicon films. The third film UF3 may also be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film. The third film UF3 may also be composed of stacked silicon oxide films and silicon carbonitride films. The third film UF3 may also be a laminated film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.

[0076] Part or all of the undercoat film UF may be formed within the processing chamber 102 of the thermal processing apparatus 100, or may be formed using other systems, such as a plasma processing system (see Figures 2 and 3) or a liquid processing system (see Figure 4).

[0077] (Step ST2: Formation of Metal-Containing Resist Film) Next, in step ST2, a metal-containing resist film RM is formed on the undercoat film UF of the substrate W. In step ST2, a metal-containing precursor having a photosensitive group and a polyfunctional compound can be used to form the metal-containing resist film RM on the undercoat film UF. The photosensitive group refers to a group that can be eliminated by exposure due to the photosensitivity of an adjacent metal atom. Examples of the photosensitive group include a hydrogen atom and a hydrocarbon group g1 that may be substituted with a halogen or the like. Examples of the hydrocarbon group g1 that may be substituted include linear or branched alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, and a t-butyl group, and -CH ｘ F ｙ(wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3), and the like.

[0078] 8 is a diagram showing an example of the cross-sectional structure of a substrate W on which a metal-containing resist film RM is formed in step ST2. As shown in FIG. 8, the metal-containing resist film RM is formed on the surface of the base film UF. The metal-containing resist film RM is a film containing a metal. In one embodiment, the metal-containing resist film RM contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In. In one example, the metal-containing resist film RM may contain Sn.

[0079] In one embodiment, the metal-containing resist film RM contains a compound having a repeating unit represented by the following formula (1) in the molecule: -(M-X-A-X)- (1) (In formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from a terminal functional group of a polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate, and A represents a divalent organic group having from 2 to 10 carbon atoms).

[0080] In one example, the divalent group derived from the terminal of the polyalcohol contains an alkoxy bond. In one example, the divalent group derived from the terminal of the polythiol contains a sulfide bond. In one example, the divalent group derived from the terminal of the polycarboxylic acid contains an ester bond. In one example, the divalent group derived from the terminal of the polyisocyanate contains a urethane bond. In one example, the divalent group derived from the terminal of the polyisothiocyanate contains a thiourethane bond. Examples of divalent organic groups that can provide A in formula (1) include an optionally substituted hydrocarbon group g2 having 2 to 10 carbon atoms. Examples of the optionally substituted hydrocarbon group g2 include linear, branched, or cyclic divalent hydrocarbon groups. Examples of the linear, branched, or cyclic divalent hydrocarbon groups may include linear, branched, or cyclic alkylene groups or arylene groups. The linear, branched, or cyclic alkylene groups and arylene groups may each have at least one hydrogen atom in the molecule substituted with a halogen or the like.

[0081] In one example, the repeating unit represented by formula (1) may have M=Sn, X=—S—, and A=ethylene group, and an exemplary process for obtaining a compound having such a repeating unit is shown in FIG. 9. In the example of FIG. 9, the metal-containing precursor having a photosensitive group is n-butyltris(dimethylamino)tin, and the polyfunctional compound is ethanedithiol. That is, in the example of FIG. 9, n-butyltris(dimethylamino)tin reacts with ethanedithiol to give —(Sn—S—CH ２ CH ２ A compound having a repeating unit represented by —S— is obtained.

[0082] In one embodiment, step ST2 can be performed by dry film formation. In the dry film formation, for example: In one embodiment, the metal-containing precursor can include a compound (α) having an amine group and / or an alkoxy group; In one embodiment, the compound (α) can include a compound (α1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In; In one embodiment, the compound (α1) can include Sn; In one embodiment, the photosensitive group in the metal-containing precursor can be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, or a —CH ｘ F ｙ (wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3); In one embodiment, the polyfunctional compound may comprise at least one compound (β) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates; In one embodiment, in step (b), H ２ O, H ２ O ２ , O ３ , and O ２ At least one selected from the group consisting of:

[0083] In the dry film formation, the formation of the metal-containing resist film RM in step ST2 may be performed using various methods such as atomic layer deposition (hereinafter referred to as "ALD method"), CVD method, etc. Various methods for forming the metal-containing resist film RM will be described below.

[0084] (ALD Method) In one embodiment, the ALD method forms a metal-containing resist film RM by self-limitingly adsorbing and reacting a predetermined material on an underlayer UF of the substrate W. In one embodiment, the step (b) can include: (b1) supplying a gas containing a metal-containing precursor onto the underlayer UF to form a metal-containing precursor film; and (b2) supplying a gas containing a polyfunctional compound to the metal-containing precursor film to form a metal-containing resist film from the metal-containing precursor film. In one embodiment, the steps (b1) and (b2) can be repeated multiple times.

[0085] 10 is a flowchart illustrating an example of process ST2 using the ALD method. As shown in FIG. 10, process ST2 using the ALD method includes a process ST211 for forming a metal-containing precursor film, a first purge process ST212, a process ST213 for forming a metal-containing film from the metal-containing precursor film, a second purge process ST214, and a determination process ST215. Note that the first purge process ST212 and the second purge process ST214 may or may not be performed. FIG. 11 is a diagram schematically illustrating an example of a phenomenon occurring on the surface of a substrate W in process ST21 using the ALD method.

[0086] 11, in step ST211, a first gas G1 containing a metal-containing precursor is supplied to the surface of the base film UF to form a metal-containing precursor film PF. In one embodiment, the metal-containing precursor includes a compound (α) having an amine group and / or an alkoxy group. The amine group is —NR ａ R ｂ where R ａ and R ｂeach independently represents an alkyl group having 1 to 2 carbon atoms. Examples of the amine group include a dimethylamino group, a diethylamino group, and an ethylmethylamino group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an i-propoxy group, and a t-butoxy group. In one embodiment, the compound (α) may include a compound (α1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In. In one embodiment, the compound (α1) may include Sn. In one embodiment, the photosensitive group in the metal-containing precursor may be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, or —CH ｘ F ｙ (wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3). For example, the metal-containing precursor may include at least one compound selected from the group consisting of an aminotin compound, an aminotitanium compound, an aminohafnium compound, an aminozirconium compound, and an aminoindium compound. Examples of the aminotin compound may include n-butyltris(dimethylamino)tin, t-butyltris(dimethylamino)tin, bis(dimethylamino)dimethyltin, bis(dimethyl)dibutyltin, azidotrimethyltin, bis(dimethylamino)dibutyltin, etc. Examples of the alkoxytin compound may include bis(tert-butoxide)dimethyltin, bis(dimethoxy)dimethyltin. Examples of the aminotitanium compound, aminohafnium compound, and aminozirconium compound include MR ｘ L ｙ (wherein M is Ti, Hf or Zr, R is a photosensitive group, L is an amine group or an alkoxy group capable of reacting with a polyfunctional compound, and x and y satisfy x≧1 and y=4−x). An example of an aminoindium compound is InR ｘ L ｙ(wherein R is a photosensitive group, L is an amine group or an alkoxy group capable of reacting with a polyfunctional compound, and x and y satisfy x≧1 and y=3−x). In one embodiment, the photosensitive group in the metal-containing precursor is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and —CH ｘ F ｙ (wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3).

[0087] In one embodiment, in step ST211, a first gas G1 is supplied into the processing chamber 102 via the gas nozzle 141. Then, in the processing chamber 102, a metal-containing precursor of the first gas G1 is adsorbed onto the surface of the underlayer film UF to form a metal-containing precursor film PF. The metal-containing precursor film PF may contain, for example, Sn, Ti, Hf, Zr, In, or the like. The metal-containing precursor film PF may be a metal complex. The metal complex may contain, for example, aminotin.

[0088] In step ST212, the gas in the processing chamber 102 is exhausted from the exhaust port 131 by the exhaust mechanism 132. At this time, an inert gas or the like may be supplied to the substrate W. This purges excess gas such as a metal-containing precursor. Examples of the inert gas include a noble gas such as He, Ar, Ne, Kr, or Xe, or nitrogen gas.

[0089] In step ST213, as shown in FIG. 11 , a second gas G2 containing a polyfunctional compound is supplied to the surface of the substrate W. The second gas G2 reacts with the metal-containing precursor film PF to form a metal-containing resist film from the metal-containing precursor film PF. The second gas G2 reacts with the metal-containing precursor adsorbed on the surface of the base film UF. Water and hydrogen peroxide are not included in the polyfunctional compound. In one embodiment, a divalent or higher-valent compound (having two or more functional groups) may be used as the polyfunctional compound. In one embodiment, the polyfunctional compound may be divalent or trivalent or higher. In one embodiment, the polyfunctional compound may include at least one compound (β) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates. Examples of polyalcohols may include ethylene glycol, glycerin, etc. Examples of polythiols may include ethanedithiol, toluenedithiol, etc. Examples of polycarboxylic acids may include glutaric acid, adipic acid, terephthalic acid (solution), etc. Examples of polyisocyanates may include toluene diisocyanate, etc. Examples of polyisothiocyanates may include butane diisothiocyanate, phenylene bis(isothiocyanate), etc. In one embodiment, in step ST213, a second gas G2 is supplied into the processing chamber 102 through the gas nozzle 141. In one embodiment, the second gas G2 is H ２ O gas, H ２ O ２ , O ３ and O ２ In one embodiment, the compound may include at least one selected from the group consisting of: ２ O gas, H ２ O ２ , O ３ and O ２ At least one selected from the group consisting of is supplied into the processing chamber 102 as a gas different from the second gas G2. Then, in the processing chamber 102, the second gas G2 reacts with the metal-containing precursor film PF to form a metal-containing resist film.

[0090] In step ST214, the gas in the processing chamber 102 is exhausted from the exhaust port 131 by the exhaust mechanism 132. At this time, an inert gas or the like may be supplied to the substrate W. This allows excess gases such as the second gas G2 to be purged.

[0091] In step ST215, it is determined whether a given condition for ending step ST21 is met. The given condition may be that a cycle of steps ST211 to ST214 has been performed a predetermined number of times. The number of times may be once, less than five times, five or more times, or ten or more times. If it is determined that the given condition is not met in step ST215, the process returns to step ST211. If it is determined that the given condition is met, step ST21 ends. For example, the given condition may be a condition regarding the dimensions of the metal-containing resist film after step ST214. That is, after step ST214, it may be determined whether the dimensions of the metal-containing resist film (resist film thickness) have reached a given value or range, and the cycle from step ST211 to step ST214 may be repeated until the given value or range is reached. The dimensions of the metal-containing resist film may be measured using an optical measurement device. As a result, a metal-containing resist film is formed on the base film UF.

[0092] (CVD method) In one embodiment, in the CVD method, a metal-containing resist film is formed by a mixed gas GM containing a metal-containing precursor and a polyfunctional compound. The metal-containing precursor may be a known metal-containing precursor (e.g., a silicon-containing compound in an example containing Si) that can be used in the CVD method, or may be a metal-containing precursor described in the ALD method. The polyfunctional compound may be a polyfunctional compound described in the ALD method. The mixed gas GM contains H ２ O, H ２ O ２ , O ３ , and O ２ In one embodiment, the mixed gas GM is supplied into the processing chamber 102 through the gas nozzle 141. The mixed gas GM chemically reacts on the substrate W, thereby forming a metal-containing resist film on the undercoat film UF.

[0093] In step ST2, the temperature and pressure of the substrate support part 121 may be set as appropriate. The temperature of the substrate support part 121 may be adjusted by controlling the output of one or more of the heaters. The temperature of the substrate support part 121 may be, for example, 25 to 350° C., and in one example, 50 to 200° C. The pressure inside the processing chamber 102 may be, for example, 500 Torr or less.

[0094] In one embodiment, step ST2 may include a step of heating and baking the metal-containing resist film. The baking may be performed in an air atmosphere or an inert atmosphere. The baking may be performed by heating the substrate W to a temperature of 50° C. or higher and 350° C. or lower, 50° C. or higher and 200° C. or lower, or 80° C. or higher and 150° C. or lower. In one embodiment, each heater of the thermal processing apparatus 100 may function as a heating unit that performs baking. In one embodiment, the baking may be performed using a thermal processing system other than the thermal processing apparatus 100.

[0095] In one embodiment, the present processing method may be performed by a dry process using a plasma processing system (see FIGS. 2 and 3). For example, a substrate W may be provided on a substrate support 11 in a processing chamber 10 of the plasma processing apparatus 1 (step ST1), and a processing gas may be supplied from a gas supply unit 20 into the processing chamber 10 to form a metal-containing resist film RM (step ST2).

[0096] When a plasma processing system is used, the above-described ALD method or CVD method may be used in step ST2. The composition (type, flow rate, and flow rate ratio) of the process gas (first gas G1, second gas G2, mixed gas GM, etc.) and the temperature of the substrate support 11 in step ST2 may be the same as when a heat processing system is used. The temperature of the substrate support 11 may be adjusted by controlling the pressure of a heat transfer gas (e.g., He) between the temperature control module or the electrostatic chuck 1111 and the backside of the substrate W. In steps ST21 and ST22, plasma may or may not be generated from the process gas. As in the case of using a heat processing system (see FIG. 1), step ST21 and / or step ST22 may include a step of heating the substrate W to perform a bake process. The bake process may be performed using, for example, a heat processing system.

[0097] In one embodiment, the present processing method may be performed by a wet process (wet film formation) using a liquid processing system (see FIG. 4 ). That is, a substrate W may be provided on a spin chuck 311 in a processing chamber 310 of a liquid processing apparatus 300 (step ST1), and a film formation solution (resist precursor liquid) may be applied onto the substrate W from a processing liquid supply nozzle 331 to form a metal-containing resist film RM (step ST2). In one embodiment, when step ST2 is performed by wet film formation, for example: in one embodiment, step (b) includes a step of applying a solution containing a metal-containing precursor and a polyfunctional compound onto an undercoat film, and a step of heating the applied solution; in one embodiment, the metal-containing precursor includes a metal complex containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In; in one embodiment, the polyfunctional compound includes at least one compound (β) selected from the group consisting of a polyalcohol, a polythiol, a polycarboxylic acid, a polyisocyanate, and a polyisothiocyanate.

[0098] When a liquid processing system is used, in step ST2, the film-forming solution (resist precursor liquid) may contain a metal-containing precursor. In one embodiment, the metal-containing precursor contains a compound (α) having an amine group. In one embodiment, the compound (α) may contain a compound (α1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In. In one embodiment, the compound (α1) may contain Sn. In one embodiment, the photosensitive group in the metal-containing precursor is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, or a —CH ｘ F ｙ (wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3). For example, the metal-containing precursor may include at least one compound selected from the group consisting of an aminotin compound, an aminotitanium compound, an aminohafnium compound, an aminozirconium compound, and an aminoindium compound. Examples of the aminotin compound may include n-butyltris(dimethylamino)tin, t-butyltris(dimethylamino)tin, bis(dimethylamino)dimethyltin, bis(dimethyl)dibutyltin, azidotrimethyltin, bis(dimethylamino)dibutyltin, etc. Examples of the alkoxytin compound may include bis(tert-butoxide)dimethyltin, bis(dimethoxy)dimethyltin. Examples of the aminotitanium compound, aminohafnium compound, and aminozirconium compound include MR ｘ L ｙ (wherein M is Ti, Hf or Zr, R is a photosensitive group, L is an amine group or an alkoxy group capable of reacting with a polyfunctional compound, and x and y satisfy x≧1 and y=4−x). An example of an aminoindium compound is InR ｘ L ｙ (wherein R is a photosensitive group, L is an amine group or an alkoxy group capable of reacting with a polyfunctional compound, and x and y satisfy x≧1 and y=3−x).

[0099] When a liquid processing system is used, in step ST2, the film-forming solution (resist precursor liquid) may contain a polyfunctional compound. In one embodiment, the polyfunctional compound may contain at least one compound (β) selected from the group consisting of polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, and polyisothiocyanate. Examples of polyalcohols may include ethylene glycol, glycerin, etc. Examples of polythiols may include ethanedithiol, toluenedithiol, etc. Examples of polycarboxylic acids may include glutaric acid, adipic acid, terephthalic acid (solution), etc. Examples of polyisocyanates may include toluene diisocyanate, etc. Examples of polyisothiocyanates may include butane diisothiocyanate, phenylene bis(isothiocyanate), etc. The second gas G2 is H ２ O, H ２ O ２ , O ３ , and O ２ The composition may include at least one selected from the group consisting of:

[0100] When a liquid processing system is used, step ST2 may include a step of heating and baking the substrate W after the solution has been applied to the substrate W. In one embodiment, the baking may be performed using, for example, a heat treatment system (see FIG. 1 ). The baking may be performed in an air atmosphere or an inert atmosphere. The baking may be performed by heating the substrate W to a temperature of 50° C. or higher and 350° C. or lower, 50° C. or higher and 200° C. or lower, or 80° C. or higher and 150° C. or lower.

[0101] In one embodiment, the deposition of the metal-containing resist film RM (step ST2) in this processing method may be performed by both a dry process using a heat treatment system (see FIG. 1) or a plasma treatment system (see FIGS. 2 and 3), and a wet process using a liquid treatment system (see FIG. 4).

[0102] In one embodiment, the reaction between the metal-containing precursor and the polyfunctional compound in step ST2 results in the metal-containing precursors being bonded to each other via a structure derived from the polyfunctional compound, thereby reducing the metal composition ratio and film density in the metal-containing resist film. The reduced metal composition ratio and film density tend to facilitate the reaction in subsequent development, even when using not only highly reactive substances (e.g., highly corrosive substances such as hydrogen chloride, boron chloride, and hydrogen bromide) but also, for example, organic acids, as described below, to form a metal-containing resist film. In one embodiment, the bonding between the metal-containing precursors to each other via a structure derived from the polyfunctional compound results in a chemical structure with a relatively weak bond strength, such as -Sn-X-A-X-Sn- (where X and A are the same as those in formula (1) above), compared to conventional bonds such as -Sn-O-Sn-, and also reduces film density, thereby tending to improve reactivity in subsequent development. In one embodiment, the type of polyfunctional compound used can be changed over time during the reaction between the metal-containing precursor and the polyfunctional compound in step ST2. As a specific example, a polyfunctional compound having a first carbon number is used in the early stage of the reaction (from the start of the reaction to a first elapsed time). Then, in the middle stage of the reaction (from the first elapsed time to a second elapsed time), a polyfunctional compound having a second carbon number greater than the first carbon number is used. Furthermore, in the later stage of the reaction (from the second elapsed time to the end of the reaction), a polyfunctional compound having a third carbon number greater than the second carbon number is used. In such an example, a metal-containing resist film having a composition and / or density gradient in the film formation direction (a metal-containing resist film in which the lower layer side has a high density (high metal composition ratio) and the upper layer side has a low density (low metal composition ratio)) is obtained. From a similar perspective, as another specific example, a polyfunctional compound having a first functionality is used in the early stage of the reaction. Then, in the middle stage of the reaction, a polyfunctional compound having a second functionality less than the first functionality is used. Furthermore, in the later stage of the reaction, a polyfunctional compound having a third functionality less than the second functionality is used.Even in such an example, a metal-containing resist film having a density gradient in the film formation direction (a metal-containing resist film in which the lower layer side has a high density (high metal composition ratio) and the upper layer side has a low density (low metal composition ratio)) can be obtained.

[0103] Whether the present processing method is carried out by dry deposition or wet deposition, in one embodiment, the present processing method can further include the steps of (c) exposing the substrate after step (b) to form exposed first regions and unexposed second regions in the metal-containing resist film, and (d) developing the substrate to selectively remove the second regions from the metal-containing resist film.

[0104] In one embodiment, in step (d), the second region can be removed by a developing gas or a developing solution. In one embodiment, the developing gas or the developing solution can contain an organic acid. In one embodiment, the organic acid can contain at least one selected from the group consisting of alcohol, thiol, carboxylic acid, sulfonic acid, β-dicarbonyl compound, alkyl carbonate, and azole, and when such an organic acid is used, the contrast of development tends to be improved. An example of the alcohol is nonafluoro-tert-butyl alcohol ((CF ３ ) ３ Examples of thiols include methanethiol, allyl mercaptan, -trifluoroethanethiol, etc. Examples of carboxylic acids include formic acid (HCOOH), acetic acid (CH ３ COOH), trichloroacetic acid (CCl ３ COOH), monofluoroacetic acid (CFH ２ COOH), difluoroacetic acid (CF ２ FCOOH), trifluoroacetic acid (CF ３ COOH) chloro-difluoroacetic acid (CClF ２ COOH), sulfur-containing acetic acid, thioacetic acid (CH ３ COSH), thioglycolic acid (HSCH ２ COOH), trifluoroacetic anhydride ((CF ３ CO) ２ O), acetic anhydride ((CH３ CO) ２ Examples of sulfonic acids include methanesulfonic acid, fluorosulfonic acid, 10-camphorsulfonic acid, etc. Examples of β-dicarbonyl compounds include acetylacetone (CH ３ C(O)CH ２ C(O)CH ３ ), trichloroacetylacetone (CCl ３ C(O)CH ２ C(O)CH ３ ), hexachloroacetylacetone (CCl ３ C(O)CH ２ C(O)CCl ３ ), trifluoroacetylacetone (CF ３ C(O)CH ２ C(O)CH ３ ), hexafluoroacetylacetone (HFAc, CF ３ C(O)CH ２ C(O)CF ３ ) and the like. An example of an alkyl carbonate may include dimethyl carbonate and the like. An example of an azole may include 1,2,3-triazole and the like. The developing gas or developing solution may include an inorganic acid. In one embodiment, the developing gas may include a halogen-containing gas. The halogen-containing gas may be a gas containing a halogen-containing inorganic acid, and may be a gas containing Br or Cl. An example of the gas containing a halogen-containing inorganic acid is HBr gas, BCl ３ The processing gas is at least one selected from the group consisting of HCl gas, HF gas, and HI gas. In one embodiment, the processing gas is a mixed gas of carboxylic acid and hydrogen halide or a mixed gas of acetic acid and formic acid. In one embodiment, the developer may be a liquid containing the above-mentioned halogen-containing inorganic acid.

[0105] In one embodiment, in step (d), the second region can be removed using a developing gas or developer solution containing a weak acid. In one embodiment, the weak acid can include an organic acid having an acid dissociation constant (pKa) of less than 16. For example, an organic acid having an acid dissociation constant (pKa) of less than 16 can be selected from the organic acids described above. In one embodiment, the weak acid can include an organic acid having an acid dissociation constant (pKa) of 0 or more and less than 16. For example, an organic acid having an acid dissociation constant (pKa) of 0 or more and less than 16 can be selected from the organic acids described above.

[0106] (Metal-Containing Resist-Forming Composition) In one embodiment, the present processing method can use a metal-containing resist-forming composition that includes a metal-containing precursor having a photosensitive group and a polyfunctional compound, where the metal-containing precursor includes a compound having a photosensitive group and an amine group and / or an alkoxy group. The metal-containing precursor and polyfunctional compound in the metal-containing resist-forming composition can be the same as those described in step ST2. In one embodiment, the metal-containing resist-forming composition can be a gas mixture of a gas containing the metal-containing precursor and a gas containing the polyfunctional compound. In one embodiment, the metal-containing resist-forming composition can be a liquid mixture of a liquid containing the metal-containing precursor and a liquid containing the polyfunctional compound.

[0107] (Metal-Containing Resist) In one embodiment, the metal-containing resist film obtained by the present processing method may contain the following metal-containing resist. That is, in one embodiment, the metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in its molecule: -(M-X-A-X)- (1) (In formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from the terminal of a polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate, and A represents a divalent organic group having from 2 to 10 carbon atoms.)

[0108] The polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, and polyisothiocyanate that can provide X in formula (1) may be the same as those described in step ST2. In one example, the divalent group derived from the terminal of the polyalcohol contains an alkoxy bond. In one example, the divalent group derived from the terminal of the polythiol contains a sulfide bond. In one example, the divalent group derived from the terminal of the polycarboxylic acid contains an ester bond. In one example, the divalent group derived from the terminal of the polyisocyanate contains a urethane bond. In one example, the divalent group derived from the terminal of the polyisothiocyanate contains a thiourethane bond.

[0109] Examples of divalent organic groups that can provide A in formula (1) include optionally substituted hydrocarbon groups g2 having 2 to 10 carbon atoms. Examples of optionally substituted hydrocarbon groups g2 include linear, branched, or cyclic divalent hydrocarbon groups. Examples of linear, branched, or cyclic divalent hydrocarbon groups may include linear, branched, or cyclic alkylene groups and arylene groups. In each of the linear, branched, or cyclic alkylene groups and arylene groups, at least one hydrogen atom in the molecule may be substituted with a halogen or the like.

[0110] 12 is a block diagram illustrating an example of the configuration of a substrate processing system SS according to an exemplary embodiment. The substrate processing system SS includes a first carrier station CS1, a first processing station PS1, a first interface station IS1, an exposure apparatus EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a controller CT.

[0111] The first carrier station CS1 transfers the first carrier C1 between the first carrier station CS1 and a system external to the substrate processing system SS. The first carrier station CS1 has a mounting table including a plurality of first mounting plates ST1. The first carrier C1, which may contain a plurality of substrates W or be empty, is mounted on each first mounting plate ST1. The first carrier C1 has a housing capable of housing a plurality of substrates W therein. The first carrier C1 is, for example, a front opening unified pod (FOUP).

[0112] The first carrier station CS1 also transports substrates W between the first carrier C1 and the first processing station PS1. The first carrier station CS1 further includes a first transport device HD1. The first transport device HD1 is provided in the first carrier station CS1 so as to be positioned between the mounting table and the first processing station PS1. The first transport device HD1 transports and hands over substrates W between the first carrier C1 on each first loading tray ST1 and the second transport device HD2 of the first processing station PS1. The substrate processing system SS may further include a load lock module. The load lock module may be provided between the first carrier station CS1 and the first processing station PS1. The internal pressure of the load lock module can be switched between atmospheric pressure and vacuum. "Atmospheric pressure" may refer to the internal pressure of the first transport device HD1. The "vacuum" refers to a pressure lower than atmospheric pressure, and may be a medium vacuum of, for example, 0.1 Pa to 100 Pa. The interior of the second transport device HD2 may be atmospheric pressure or a vacuum. The load lock module may, for example, transport a substrate W from the first transport device HD1 at atmospheric pressure to the second transport device HD2 at vacuum, and may also transport a substrate W from the second transport device HD2 at vacuum to the first transport device HD1 at atmospheric pressure.

[0113] The first processing station PS1 performs various processes on the substrates W. In one embodiment, the first processing station PS1 includes a pre-processing module PM1, a resist film formation module PM2, and a first thermal processing module PM3 (hereinafter collectively referred to as "first substrate processing modules PMa"). The first processing station PS1 also includes a second transport device HD2 that transports the substrates W. The second transport device HD2 transports and transfers the substrates W between two designated first substrate processing modules PMa, and between the first processing station PS1 and the first carrier station CS1 or the first interface station IS1.

[0114] In the pre-treatment module PM1, the substrate W is subjected to pre-treatment. In one embodiment, the pre-treatment module PM1 includes a temperature adjustment unit that adjusts the temperature of the substrate W, a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision, and a base film formation unit that forms a part or all of a base film on the substrate W. In one embodiment, the pre-treatment module PM1 includes a surface modification unit that performs a surface modification treatment on the substrate W. Each treatment unit in the pre-treatment module PM1 may include a heat treatment apparatus 100 (see FIG. 1), a plasma treatment apparatus 1 (see FIGS. 2 and 3), and / or a liquid treatment apparatus 300 (see FIG. 4).

[0115] In the resist film formation module PM2, a resist film is formed on the substrate W. In one embodiment, the resist film formation module PM2 includes a dry coating unit. The dry coating unit forms a resist film on the substrate W using a dry process such as a vapor phase deposition method. In one example, the dry coating unit includes a CVD apparatus or an ALD apparatus that performs chemical vapor deposition of a resist film on the substrate W arranged in a chamber, or a PVD apparatus that performs physical vapor deposition of a resist film. The dry coating unit may be a thermal processing apparatus 100 (see FIG. 1) or a plasma processing apparatus 1 (see FIGS. 2 and 3).

[0116] In one embodiment, the resist film formation module PM2 includes a wet coating unit that forms a resist film on the substrate W using a wet process such as a liquid deposition method. The wet coating unit may be, for example, the liquid processing apparatus 300 (see FIG. 4).

[0117] In one embodiment, an example of the resist film formation module PM2 includes both a wet coating unit and a dry coating unit.

[0118] The substrate W is subjected to a thermal treatment in the first thermal treatment module PM3. In one embodiment, the first thermal treatment module PM3 includes one or more of a pre-bake (Post Apply Bake: PAB) unit that performs a heat treatment on the substrate W on which a resist film has been formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1 ). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0119] The first interface station IS1 has a third transport device HD3. The third transport device HD3 transports and transfers substrates W between the first processing station PS1 and the exposure apparatus EX. The third transport device HD3 has a housing that houses the substrates W, and may be configured so that the temperature, humidity, pressure, etc. within the housing can be controlled.

[0120] The exposure apparatus EX uses an exposure mask (reticle) to expose a resist film on the substrate W. The exposure apparatus EX may be, for example, an EUV exposure apparatus having a light source that generates EUV light.

[0121] The second interface station IS2 has a fourth transport device HD4. The fourth transport device HD4 transports and transfers substrates W between the exposure apparatus EX and the second processing station PS2. The fourth transport device HD4 has a housing that houses the substrates W, and may be configured so that the temperature, humidity, pressure, etc. within the housing can be controlled.

[0122] The second processing station PS2 performs various processes on the substrates W. In one embodiment, the second processing station PS2 includes a second thermal processing module PM4, a measurement module PM5, a development module PM6, and a third thermal processing module PM7 (hereinafter collectively referred to as "second substrate processing modules PMb"). The second processing station PS2 also includes a fifth transport device HD5 that transports the substrates W. The fifth transport device HD5 transports and transfers the substrates W between two designated second substrate processing modules PMb, and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2.

[0123] The substrate W is subjected to a thermal treatment in the second thermal treatment module PM4. In one embodiment, the thermal treatment module PM4 includes one or more of a post-exposure bake (PEB) unit that heat-treats the exposed substrate W, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1 ). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0124] In the measurement module PM5, various measurements are performed on the substrate W. In one embodiment, the measurement module PM5 includes an imaging unit including a mounting table on which the substrate W is placed, an imaging device, an illumination device, and various sensors (temperature sensor, reflectance measurement sensor, etc.). The imaging device may be, for example, a CCD camera that captures an image of the appearance of the substrate W. Alternatively, the imaging device may be a hyperspectral camera that captures images by dispersing light into wavelengths. The hyperspectral camera can measure one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.

[0125] In the developing module PM6, the substrate W is subjected to a development process. In one embodiment, the developing module PM6 includes a dry developing unit that performs dry development on the substrate W. The dry developing unit may be, for example, the thermal processing apparatus 100 (see FIG. 1) or the plasma processing apparatus 1 (see FIGS. 2 and 3). In one embodiment, the developing module PM6 includes a wet developing unit that performs wet development on the substrate W. The wet developing unit may be, for example, the liquid processing apparatus 300 (FIG. 4). In one embodiment, the developing module PM6 includes both a dry developing unit and a wet developing unit.

[0126] The substrate W is subjected to a thermal treatment in the third thermal treatment module PM7. In one embodiment, the third thermal treatment module PM7 includes one or more of a post bake (PB) unit that heat-treats the developed substrate W, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision. Each of these units may have one or more thermal treatment devices. In one example, the multiple thermal treatment devices may be stacked. The thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1 ). Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.

[0127] The second carrier station CS2 transfers the second carrier C2 between the second carrier station CS2 and a system external to the substrate processing system SS. The configuration and functions of the second carrier station CS2 may be similar to those of the first carrier station CS1 described above.

[0128] The controller CT controls each component of the substrate processing system SS to perform a given process on the substrate W. The controller CT stores a recipe in which a process procedure, process conditions, transport conditions, etc. are set, and controls each component of the substrate processing system SS to perform a given process on the substrate W in accordance with the recipe. The controller CT may also perform some or all of the functions of each controller (the controller 200, controller 2, and controller 400 shown in FIGS. 1 to 4).

[0129] 13 is a flowchart showing a substrate processing method (hereinafter also referred to as "method MT") according to an exemplary embodiment. As shown in FIG. 13, method MT includes a process ST100 for pre-treating a substrate, a process ST200 for forming a resist film on the substrate, a process ST300 for performing a heat treatment (pre-bake: PAB) on the substrate on which the resist film has been formed, a process ST400 for exposing the substrate to EUV light, a process ST500 for performing a heat treatment (post-exposure bake: PEB) on the exposed substrate, a process ST600 for measuring the substrate, a process ST700 for developing the resist film on the substrate, a process ST800 for performing a heat treatment (post-bake: PB) on the developed substrate, and a process ST900 for etching the substrate. Method MT does not necessarily include one or more of the above processes. For example, the method MT may not include step ST600, and step ST700 may be performed after step ST500.

[0130] The method MT may be performed using a substrate processing system SS shown in Fig. 12. In the following, an example will be described in which a controller CT of the substrate processing system SS controls each part of the substrate processing system SS to perform the method MT on a substrate W.

[0131] (Process ST100: Pretreatment) First, a first carrier C1 containing a plurality of substrates W is loaded into a first carrier station CS1 of the substrate processing system SS. The first carrier C1 is placed on a first mounting plate ST1. Next, the first transport device HD1 sequentially removes each substrate W from the first carrier C1 and transfers them to a second transport device HD2 of the first processing station PS1. The substrates W are transported by the second transport device HD2 to a pretreatment module PM1. The pretreatment module PM1 subjects the substrates W to pretreatment. The pretreatment may include, for example, one or more of temperature adjustment of the substrate W, forming a part or all of an underlayer film on the substrate W, heating the substrate W, and high-precision temperature adjustment of the substrate W. As another example, the pretreatment may include a surface modification process of the substrate W.

[0132] (Process ST200: Resist Film Formation) Next, the substrate W is transported to the resist film formation module PM2 by the second transport device HD2. A resist film is formed on the substrate W by the resist film formation module PM2. In one embodiment, the resist film is formed by a wet process such as a liquid phase deposition method. For example, a resist film is formed by spin-coating a resist film on the substrate W using a wet coating unit of the resist film formation module PM2. In one embodiment, the resist film is formed on the substrate W by a dry process such as a vapor phase deposition method. For example, a resist film is formed by vapor-depositing a resist film on the substrate W using a dry coating unit of the resist film formation module PM2. The formation of the resist film in process ST200 may be performed using the present processing method (see FIG. 5 ). That is, a metal-containing resist film RM may be formed on the substrate W.

[0133] The resist film may be formed on the substrate W using both a dry process and a wet process. For example, after a first resist film is formed on the substrate W by a dry process, a second resist film may be formed on the first resist film by a wet process. In this case, the film thickness, material, and / or composition of the first resist film and the second resist film may be the same or different.

[0134] (Process ST300: PAB) Next, the substrate W is transported by the second transport device HD2 to the first thermal treatment module PM3. The first thermal treatment module PM3 subjects the substrate W to a heating treatment (pre-baking: PAB). The pre-baking may be performed in an air atmosphere or an inert atmosphere. The pre-baking may be performed by heating the substrate W to 50° C. or higher or 80° C. or higher. The heating temperature of the substrate W may be 250° C. or lower, 200° C. or lower, or 150° C. or lower. In one example, the heating temperature of the substrate may be 50° C. or higher and 250° C. or lower. When a resist film is formed by a dry process in process ST200, in one embodiment, the pre-baking may be performed in the dry coating unit that performed process ST200. In one embodiment, after the pre-baking, a process (Edge Bead Removal: EBR) for removing the resist film from the edge of the substrate W may be performed.

[0135] (Process ST400: EUV Exposure) Next, the substrate W is transferred by the second transport device HD2 to the third transport device HD3 in the first interface station IS1. The substrate W is then transported by the third transport device HD3 to the exposure apparatus EX. The substrate W is subjected to EUV exposure via an exposure mask (reticle) in the exposure apparatus EX. EUV has a wavelength in the range of 10 to 20 nm, for example. EUV may have a wavelength in the range of 11 to 14 nm, and in one example has a wavelength of 13.5 nm. As a result, a first region that is EUV exposed and a second region that is not EUV exposed are formed on the substrate W, corresponding to the pattern of the exposure mask (reticle). In one embodiment, the film thickness of the first region may be smaller than the film thickness of the second region 2.

[0136] (Process ST500: PEB) Next, the substrate W is transferred from the fourth transport device HD4 in the second interface station IS2 to the fifth transport device HD5 in the second processing station PS2. The substrate W is then transported by the fifth transport device HD5 to the second thermal treatment module PM4. The substrate W is then subjected to a heat treatment (post-exposure bake: PEB) in the second thermal treatment module PM4. The post-exposure bake may be performed in an air atmosphere. Alternatively, the post-exposure bake may be performed by heating the substrate W to a temperature of 180° C. or higher and 250° C. or lower.

[0137] (Process ST600: Measurement) Next, the substrate W is transported to the measurement module PM5 by the fifth transport device HD5. The measurement module PM5 measures the substrate W. The measurement may be optical measurement or other measurement. In one embodiment, the measurement by the measurement module PM5 includes measurement of the appearance and / or dimensions of the substrate W using a CCD camera. In one embodiment, the measurement by the measurement module PM5 includes measurement of one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.") using a hyperspectral camera.

[0138] In one embodiment, the controller CT determines whether or not there is an exposure abnormality in the substrate W based on the measured appearance, dimensions, and / or pattern shape of the substrate W. In one embodiment, if the controller CT determines that there is an exposure abnormality, the substrate W may be reworked or discarded without being developed in step ST700. Reworking of the substrate W may be performed by removing the resist on the substrate W and returning to step ST200 to form a resist film again. Reworking after development may cause damage to the substrate W, but by performing rework before development, damage to the substrate W can be avoided or suppressed.

[0139] (Step ST700: Development) Next, the substrate W is transported to the developing module PM6 by the fifth transport device HD5. In the developing module PM6, the resist film on the substrate W is developed. Either the first region exposed to EUV or the second region not exposed to EUV is selectively removed by development. The development process may be performed by dry development or wet development. The development process may be performed by a combination of dry development and wet development. After or during the development process, a desorption process may be performed one or more times. The desorption process includes descumming or smoothing the surface of the resist film using an inert gas such as helium or a plasma of the inert gas. The development process may be performed by heating the substrate W to 100° C. or higher and 350° C. or lower. The dry development process may be performed at a pressure of 10 Torr or lower. The development process may be carried out for 0.5 minutes to 2 hours. As described above, in one embodiment, the present processing method can also be carried out as part of a development method. That is, in one embodiment, the development method includes the steps of: (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film; (b) exposing the metal-containing resist through an exposure mask to form an exposed first region and an unexposed second region in the metal-containing resist; and (c) selectively removing one of the first region and the second region, wherein the metal-containing resist in the step (a) contains a compound having a repeating unit represented by the above formula (1) in its molecule.

[0140] (Step ST800: PB) Next, the substrate W is transported by the fifth transport device HD5 to the third thermal treatment module PM7, where it is subjected to a thermal treatment (post-bake). The post-bake may be performed in an air atmosphere, or in an N ２ Or O ２The post-baking may be performed in a reduced pressure atmosphere containing . Furthermore, the post-baking may be performed by heating the substrate W to 150° C. or higher and 250° C. or lower. The post-baking may be performed in the second thermal treatment module PM4 instead of the third thermal treatment module PM7. In one embodiment, after the post-baking, the measurement modules PM4 and PM5 may perform optical measurement of the substrate W. Such measurement may be performed in addition to or instead of the measurement in process ST600. In one embodiment, the controller CT determines the presence or absence of an abnormality, such as a defect, a scratch, or foreign matter adhesion, in the developed pattern of the substrate W, based on the measured appearance, dimensions, and / or pattern shape of the substrate W. In one embodiment, if the controller CT determines that an abnormality exists, the substrate W may be reworked or discarded without being etched in process ST900. In one embodiment, if the controller CT determines that an abnormality exists, the opening dimensions of the resist film on the substrate W may be adjusted using a dry coating unit (such as a CVD apparatus or an ALD apparatus).

[0141] (Process ST900: Etching) After the process ST800 is performed, the substrate W is transferred by the fifth transport device HD5 to the sixth transport device HD6 of the second carrier station CS2, and then transferred by the sixth transport device HD6 to the second carrier C2 of the second mounting tray ST2. The second carrier C2 is then transferred to a plasma processing system (not shown). The plasma processing system may be, for example, the plasma processing system shown in FIGS. 2 and 3. In the plasma processing system, the base film UF of the substrate W is etched using the developed resist film as a mask. This completes the method MT. When the resist film is developed using a plasma processing device in the process ST700, etching may be performed subsequently in a plasma processing chamber of the plasma processing device. Furthermore, if the second processing station PS2 includes a plasma processing module in addition to the developing module PM6, etching may be performed in the plasma processing module. The above-described desorption process may be performed one or more times before or during etching. As described above, in one embodiment, the present processing method can also be carried out as a part of an etching method, that is, in one embodiment, the processing method includes the steps of: (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film, wherein the metal-containing resist has at least one opening; and (b) etching the undercoat film through the opening, wherein the metal-containing resist contains a compound having a repeating unit represented by the above formula (1) in its molecule.

[0142] Embodiments of the present disclosure further include the following aspects.

[0143] (Supplementary Note 1) A substrate processing method, comprising: (a) providing a substrate having an underlayer; and (b) forming a metal-containing resist film on the underlayer using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0144] (Supplementary Note 2) The substrate processing method according to Supplementary Note 1, wherein the metal-containing precursor includes a compound (α) having an amine group and / or an alkoxy group.

[0145] (Appendix 3) The substrate processing method according to Appendix 2, wherein the compound (α) includes a compound (α1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

[0146] (Appendix 4) The substrate processing method according to Appendix 3, wherein the compound (α1) contains Sn.

[0147] (Note 5) The photosensitive group is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, or a —CH ｘ F ｙ (wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3).

[0148] (Appendix 6) The substrate processing method according to any one of Appendices 1 to 5, wherein the polyfunctional compound includes at least one compound (β) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

[0149] (Appendix 7) In the step (b), H ２ O, H ２ O ２ , O ３ , and O ２ The substrate processing method according to any one of claims 1 to 6, further comprising at least one selected from the group consisting of:

[0150] (Supplementary Note 8) The substrate processing method according to any one of Supplementary Notes 1 to 7, wherein the step (b) includes: (b1) supplying a gas containing the metal-containing precursor onto the base film to form a metal-containing precursor film; and (b2) supplying a gas containing the polyfunctional compound to the metal-containing precursor film to form the metal-containing resist film from the metal-containing precursor film.

[0151] (Supplementary Note 9) The substrate processing method according to Supplementary Note 8, wherein the steps (b1) and (b2) are repeated multiple times.

[0152] (Appendix 10) The substrate processing method according to any one of Appendices 1 to 9, wherein the step (b) includes forming the metal-containing resist film using a mixed gas containing the metal-containing precursor and the polyfunctional compound.

[0153] (Appendix 11) The substrate processing method according to any one of Appendices 1 to 10, wherein the metal-containing precursor comprises a metal complex containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

[0154] (Appendix 12) The substrate processing method according to any one of Appendices 1 to 11, wherein the polyfunctional compound includes at least one compound (β) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.

[0155] (Appendix 13) The substrate processing method according to any one of Appendices 1 to 12, wherein the step (b) includes: applying a solution containing the metal-containing precursor and the polyfunctional compound onto the base film; and heating the applied solution to form a metal-containing resist film.

[0156] (Supplementary Note 14) The substrate processing method according to any one of Supplementary Notes 1 to 13, further comprising: (c) after the step (b), exposing the substrate to light to form an exposed first region and an unexposed second region in the metal-containing resist film; and (d) developing the substrate to selectively remove the second region from the metal-containing resist film.

[0157] (Supplementary Note 15) The substrate processing method according to Supplementary Note 14, wherein in the step (d), the second region is removed by a developing gas or developing solution containing a weak acid.

[0158] (Supplementary Note 16) The substrate processing method according to Supplementary Note 15, wherein the weak acid comprises an organic acid having an acid dissociation constant (pKa) of less than 16.

[0159] (Appendix 17) The substrate processing method according to appendix 16, wherein the organic acid includes at least one selected from the group consisting of alcohols, thiols, carboxylic acids, sulfonic acids, β-dicarbonyl compounds, alkyl carbonates, and azoles.

[0160] (Appendix 18) A metal-containing resist-forming composition comprising: a metal-containing precursor having a photosensitive group; and a polyfunctional compound, wherein the metal-containing precursor comprises a compound having the photosensitive group, and an amine group and / or an alkoxy group.

[0161] (Appendix 19) A metal-containing resist comprising a compound having a repeating unit represented by the following formula (1) in its molecule: -(M-X-A-X)- (1) (In the formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from a terminal functional group of a polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate, and A represents a divalent organic group having from 2 to 10 carbon atoms.)

[0162] (Supplementary Note 20) A substrate processing system having one or more substrate processing apparatuses and a control unit, wherein the control unit is configured to perform the following control on the one or more substrate processing apparatuses: (a) control the one or more substrate processing apparatuses to provide a substrate having an underlayer film; and (b) control the one or more substrate processing apparatuses to form a metal-containing resist film on the underlayer film by using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0163] (Supplementary Note 21) A device manufacturing method, comprising: (a) providing a substrate having an underlayer; and (b) forming a metal-containing resist film on the underlayer using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0164] (Supplementary Note 22) A program causing a computer of a substrate processing system having one or more substrate processing apparatuses and a control unit to execute the following: (a) control of providing a substrate having an underlayer film; and (b) control of forming a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.

[0165] (Supplementary Note 23) A storage medium storing the program according to Supplementary Note 22.

[0166] (Supplementary Note 24) A developing method comprising the steps of: (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film; (b) exposing the metal-containing resist through an exposure mask to form an exposed first region and an unexposed second region in the metal-containing resist; and (c) selectively removing one of the first region and the second region, wherein the metal-containing resist in (a) contains a compound having a repeating unit represented by the following formula (1) in its molecule: -(M-X-A-X)- (1) (In the above formula (1), M represents Sn, Ti, Hf, Zr, or In; X represents a divalent group derived from a terminal functional group of a polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate; and A represents a divalent organic group having from 2 to 10 carbon atoms.)

[0167] (Appendix 25) An etching method comprising: (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film, wherein the metal-containing resist has at least one opening; and (b) etching the undercoat film through the opening, wherein the metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in its molecule: -(M-X-A-X)- (1) (In the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from a terminal functional group of a polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate, and A represents a divalent organic group having from 2 to 10 carbon atoms.)

[0168] The above embodiments are described for the purpose of explanation and are not intended to limit the scope of the present disclosure. Various modifications can be made to each embodiment without departing from the scope and spirit of the present disclosure. For example, some components in one embodiment can be added to other embodiments. Also, some components in one embodiment can be replaced with corresponding components in other embodiments.

[0169] 1... plasma processing apparatus, 2... control section, 10... plasma processing chamber, 1... substrate support section, 20... gas supply section, 30... power supply, 100... heat processing apparatus, 102... processing chamber, 120... stage heater, 121... substrate support section, 141... gas nozzle, 200... control section, 300... liquid processing apparatus, 311... spin chuck, 321... cup, 331... processing liquid supply nozzle, 351... cleaning liquid supply nozzle, 400... control section, RM... metal-containing resist film, UF... base film, W... substrate

Claims

1. A substrate processing method, comprising: (a) providing a substrate having an underlayer film; (b) forming a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound; and the polyfunctional compound includes at least one compound (β) selected from the group consisting of polythiol, polycarboxylic acid, polyisocyanate, and polyisothiocyanate. A substrate processing method.

2. The substrate processing method according to claim 1, wherein the metal-containing precursor includes a compound (α) having an amino group and / or an alkoxy group.

3. The substrate processing method according to claim 2, wherein the compound (α) includes a compound (α1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

4. The substrate processing method according to claim 3, wherein the compound (α1) contains Sn.

5. The photosensitive group is at least one group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and -CH x F y (wherein x represents an integer of 0 to 2 and y represents an integer of 1 to 3). The substrate processing method according to claim 1, comprising at least one group selected from the group consisting of.

6. In the step (b), at least one selected from the group consisting of H 2 O, H 2 O 2 O 3 and O 2 is further used. The substrate processing method according to claim 1.

7. The step (b) includes: (b1) supplying a gas containing the metal-containing precursor onto the underlayer film to form a metal-containing precursor film; (b2) supplying a gas containing the polyfunctional compound to the metal-containing precursor film to form the metal-containing resist film from the metal-containing precursor film; The substrate processing method according to claim 1.

8. The substrate processing method according to claim 7, wherein the steps (b1) and (b2) are repeated a plurality of times.

9. The substrate processing method according to claim 1, wherein the step (b) includes forming the metal-containing resist film using a mixed gas containing the metal-containing precursor and the polyfunctional compound.

10. The substrate processing method according to claim 1, wherein the metal-containing precursor includes a metal complex containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.

11. The step (b) includes: applying a solution containing the metal-containing precursor and the polyfunctional compound onto the underlayer film; heating the applied solution to form a metal-containing resist film; The substrate processing method according to claim 10.

12. (c) after the step (b), exposing the substrate to form an exposed first region and an unexposed second region in the metal-containing resist film; (d) developing the substrate to selectively remove the second region from the metal-containing resist film; The substrate processing method according to claim 1, further comprising

13. The substrate processing method according to claim 12, wherein in the step (d), the second region is removed by a developing gas or a developing solution containing a weak acid.

14. The substrate processing method according to claim 13, wherein the weak acid contains an organic acid having an acid dissociation constant (pKa) of less than 16.

15. The substrate processing method according to claim 14, wherein the organic acid contains at least one selected from the group consisting of alcohol, thiol, carboxylic acid, sulfonic acid, β-dicarbonyl compound, alkyl carbonate, and azole.

16. A substrate processing method, comprising: (a) providing a substrate having an underlayer film; (b) forming a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound (excluding polyhydric alcohols). having Substrate processing method.

17. A metal-containing precursor having a photosensitive group, A polyfunctional compound, comprising wherein the metal-containing precursor contains a compound having a photosensitive group, an amine group, and / or an alkoxy group, wherein the polyfunctional compound contains at least one compound (β) selected from the group consisting of polythiol, polycarboxylic acid, polyisocyanate, and polyisothiocyanate. Composition for forming a metal-containing resist.

18. A metal-containing resist comprising a compound having a repeating unit represented by the following formula (1) in the molecule. -(M-X-A-X)-(1) (In the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from a terminal functional group of polythiol, polycarboxylic acid, polyisocyanate, or polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms.)

19. A substrate processing system having one or more substrate processing apparatuses and a control unit, wherein the control unit controls to provide a substrate having an underlayer film to the one or more substrate processing apparatuses, and controls to form a metal-containing resist film on the underlayer film using a metal-containing precursor having a photosensitive group and a polyfunctional compound, and the polyfunctional compound contains at least one compound (β) selected from the group consisting of polythiol, polycarboxylic acid, polyisocyanate, and polyisothiocyanate. A substrate processing system configured to execute.

20. Step of providing a substrate having (a) an underlying film and a metal-containing resist on the underlying film Step of exposing the metal-containing resist through a photomask to form, in the metal-containing resist, an exposed first region and an unexposed second region Step of selectively removing one of the first region and the second region which includes The developing method, wherein the metal-containing resist in (a) includes a compound having a repeating unit represented by the following formula (1) in the molecule -(M-X-A-X)- (1) (In the above formula (1), M represents Sn, Ti, Hf, Zr or In; X represents a divalent group derived from a terminal functional group of polythiol, polycarboxylic acid, polyisocyanate or polyisothiocyanate; A represents a divalent organic group having 2 to 10 carbon atoms.)

21. Step of providing a substrate having (a) an underlying film and a metal-containing resist on the underlying film, wherein the metal-containing resist has at least one opening Step of etching the underlying film through the opening which includes The etching method, wherein the metal-containing resist includes a compound having a repeating unit represented by the following formula (1) in the molecule -(M-X-A-X)- (1) (In the above formula (1), M represents Sn, Ti, Hf, Zr or In; X represents a divalent group derived from a terminal functional group of polythiol, polycarboxylic acid, polyisocyanate or polyisothiocyanate; A represents a divalent organic group having 2 to 10 carbon atoms.)